Polyester fiber dyed with monoazo compound containing an acylamidotetrahydroquinoline group

ABSTRACT

A linear polyester textile fiber dyed with a water-insoluble azo compound having a 1-alkyl- or 1-cycloalkyl-7-acylamido-1,2,3,4tetrahydroquinoline coupling component and certain substituted phenyl groups as the diazo component.

nited States Patent 1191 Weaver et al.

POLYESTER FIBER DYED WITH MONOAZO COMPOUND CONTAINING AN ACYLAMIDOTETRAHYDROQUIN- OLINE GROUP lnventors; Max A. Weaver; James M. Straley;

Clarence A. Coates, Jr., all Of Kingsport, Tenn. Assignee: Eastman Kodak Company,

' Rochester, NY.

Filed: Sept. 23, 1971 Appl. No.: 183,233

Related Us. Application Data Division Of Set. No. 812,411, April 1, 1969, Pat. NO. 3,635,941.

US. Cl .Q ..8/41 C, 8/41 R, 8/41 E Int. Cl. ...D06p 1/18, C09d 29/36 51 Feb. 13, 1973 3,213,081 lO/l 965 Straleyetal ..260/155 Primary Examiner-George F. Lesmes Assistant Examiner-Patricia Ct lves Attorney'-Cecil D. Quillen, Jr. et al.

[5 7] ABSTRACT A linear polyester textile fiber dyed with a water-insoluble azO compound having al-alkyl- Or l-cycloalkyl-7-acylamidO-1 ,2,3,4-tetrahydroquinoline coupling component and certain substituted phenyl groups as the diazO component.

iU'Claims, No Drawings POLYESTER FIBER DYED WITH MONOAZO COMPOUND CONTAINING AN ACYLAMIDOTETRAI-IYDROQUINOLINE GROUP I group and-to polyester textile materials dyed therewith.

' The novel compounds of the invention have the formula D is a phenyl radical having the structure I l l X Y Z wherein V is halogen, cyano, lower alkanoyl, aroyl, lower alkylsulfonyL or trifluoromethyl;

X is nitro or cyano;

Y and Y are the same or different and each is hydrogen, cyano, or halogen;

Z is hydrogen, cyano, halogen, or lower alkylsulfonyl; and

R is lower alkyl;

A is an acyl radical;

R, R and R are the same or different and each is hydrogen or lower alkyl;

R is hydrogen, lower alkoxy or lower alkanoyloxy;

R is'hydrogen, lower alkyl or lower alkoxy; and

R is an alkyl radical, free of hydroxy and vinylsulfonyl groups, or a cycloalkyl radical.

The azo compounds of the invention produce red to turquoise shades on polyester textile materials when applied thereto according to conventional dyeing procedures. The novel azo compounds possess excellent brightness, dyeability and fastness properties. For example, the compounds possess excellent affinity for and buildup on polyester fibers. The compounds of the invention also exhibit excellent fastness to light and resistance to sublimation when tested according to the procedures described in the Technical Manual of the American Association of Textile Chemists and Colorists. For example, the novel azo compounds in general exhibit superior fastness properties, such as fastness to light, and superior brightness on polyester fibers when compared with the azo compounds disclosed in vU. S. Pat. No. 2,249,774. In describing the compounds of the invention as water-insoluble it is meant that the compounds are relatively and substantially water-insoluble due to the absence of water-solubilizing groups such as sulfo and salts thereof.

, trifluoroacetyl,

Chlorine and bromine are typical halogen atoms which V, Y and Z can represent. Examples of the alkanoyl, aroyl and alkylsulfonyl groups which V, Y and/or Z can represent and the alkylsulfonyl groups represented by RSO,- are set forth in the following definition of A. Examples of the alkyl groups represented by R appear in the definition of R hereinbelow.

The acyl groups represented by A can be formyl, lower alkanoyl, aroyl, cyclohexylcarbonyl, lower alkoxycarbonyl, aryloxycarbonyl, lower alkylsulfonyl, cyclohexylsulfonyl, arylsulfonyl, carbamoyl, lower alkylcarbamoyl, arylcarbamoyl, sulfamoyl, lower alkylsulfamoyl, furoyl, etc. The alkanoyl groups can be substituted with substituents such as halogen, aryl, cyano, lower alkoxy, benzyloxy, lower alkylthio, lower alkylsulfonyl, etc. The alkylsulfonyl groups also can be substituted, for example, with cyano, hydroxy, halogen and the like. The alkoxycarbonyl groups can be substituted, for example, with hydroxy, alkoxy and cyano. Acetyl, propionyl, butyryl, cyanoacetyl, chloroacetyl, phenylacetyl, methoxyacetyl, methylthioacetyl, methyls'ulfonylacetyl, methoxycarbonyl, propoxycarbonyl, butoxycarbonyl, methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, 2- cyanoethylsulfonyl, Z-hydroxyethylsulfonyl, and 2- chloroethylsulfonyl, are examples of the alkanoyl, alkoxycarbonyl, and alkylsulfonyl groups which A can represent. The aryl group, designated Ar, of the arylalkanoyl,'aroyl, aryloxycarbonyl, arylsulfonyl, and arylcarbamoyl groups preferably is 'monocyclic, carbocyclic aryl such as unsubstituted phenyl and phenyl substituted with, for example, lower alkyl, lower alkoxy, halogen, etc. Tolyl, anisyl, p-bromophenyl and o,pdichlorophenyl are typical of such aryl groups. Dimethylcarbamoyl, ethylcarbamoyl, propylcarbamoyl, butylcarbamoyl, and dimethylsulfamoyl are illustrative alkylcarbamoyl and alkylsulfamoyl groups which A can represent.

Methyl, ethyl, propyl, isopropyl, isobutyl, butyl, etc. are typical alkyl groups which R, R, R and R can represent. Methoxy, ethoxy, propoxy and butoxy are representative of the alkoxy groups which R and R can represent. Examples of the alkanoyloxy groups which R can represent include acetoxy, propionoxy, butyroxy, isobutyroxy, etc. As used herein to describe a group containing an alkyl moiety, lower designates a carbon content of up to about four carbon atoms. Preferably, R is methyl or, when R and R each is hydrogen, lower alkyl, and each of R, R and R is hydrogen when R is lower alkoxy or lower alkanoyloxy The alkyl radicals which R can represent can be straightor branch-chain, substituted or unsubstituted alkyl of up to about 10 carbon atoms. The unsubstituted alkyl radicals preferably contain from one to about six carbon atoms while the substituted alkyl groups preferably contain three to about eight carbon which are disclosed in U. S. Pat. No. 3,349,076 also can be present on alkyl radical R Other substituents which can be present on alkyl radical R include cyano, lower alkoxy, lower cyanoalkoxy, lower alkylthio, lower cyanoalkylthio, arylthio, cyclohexylthio, halogen, aryloxy, thiocyano, sulfamoyl, lower alkylsulfamoyl, and groups having the structure The aryl and arylene moieties of the substituents referred to in the preceding sentence can be unsubstituted phenyl or phenyl substituted, for example, with lower alkyl, lower alkoxy, or halogen. Azolethio groups such as 2-benzothiazolylthio, 1,2,4-triazol-3-ylthio, and 2-benzothi-azolylthio groups are other substituents which can be present on alkyl radical R The alkyl radicals represented by R can be substituted with an unsubstituted or substituted phenyl group. Lower alkylphenyl, lower alkoxyphenyl, halophenyl, lower alkoxycarbonylphenyl, etc. are typical of the substituted phenyl groups. Examples of phenylalkyl radicals represented by R include benzyl, 2-phenylethyl, 2-pethylphenylethyl, p-methoxycarbonylbenzyl, mchlorobenzyl, Z-p-methoxyphenylethyl, etc. The cycloalkyl radicals which R can represent preferably are cyclopentyl, cyclohexyl and lower alkyl-substituted derivatives thereof.

The following groups are typical of the substituted alkyl, cyclohexyl and aralkyl radicals represented by R 3-acetoxyethyl, 2,3-dipropionoxypropyl, 2-phenylcarbamoyloxyethyl, 2-ethoxycarbonyloxyethyl, 4- toluoyloxy, acetyl, Z-methylsulfonylethyl, 3-(2- cyanoethylsulfonyl)propyl, 3-methylsulfonylamidopropyl, 3-N-acetylmethylsulfonamidopropyl, 3-N-phenylmethylsulfonamidopropyl,

2-N-(2-cyanoethyl)-p-tolyl-sulfonamidoethyl, 3-suc' cinimidopropyl, 2-glutarimidoethyl, 2- phthalimidoethyl, 4-(2-piperidono)butyl, 2

cyanoethyl, 2-methoxyethyl, 3-sulfamoyl-propyl, 2- (lH-l ,2,4-triazol-3-yl-thio )ethyl, 3-(4-acetoxysuccinimido)propyl, 3-t0lylthiopropyl, 2-phenoxyethyl, 2-

. dimethylsulfamoylethyl, cyclohexyl, 4-ethylcyclohexyl,

2-acetoxy-3-chloropropyl, 3,3,S-trimethylcyclohexyl, benzyl, 2-phenylethyl, p-methylbenzyl, m-methoxycarbonylbenzyl, 3-cyclohexoxypropyl, 3-(2-cyanoethoxy)propyl, 3-isobutyramidopropyl, and 3-N-benzylethylsulfonamidopropyl.

Preferred compounds of the invention are those conforming to formula (I) wherein D represents a group having the formula pyrrolidinono,

wherein V is chlorine, bromine, cyano, or benzoyl;

X is nitro or cyano;

Y and Y each is hydrogen, cyano, chlorine or bromine;

Z is hydrogen, chlorine, bromine, or lower alkylsulfonyl;

R is lower alkyl;

A is lower alkanoyl, benzoyl, lower alkoxycarbonyl, lower alkylsulfonyl or lower alkylcarbamoyl;

R is methyl or, when R and R each is hydrogen, lower alkyl;

R and R each is hydrogen or methyl;

R and R each is hydrogen; and

R is lower alkyl, benzyl, 2-phenylethyl, cyclohexyl, or a substituted alkyl group having the formula -R -R wherein R is ethylene or propylene and R is lower alkanoyloxy, lower alkoxy, lower alkanoylamino, cyano, carbamoyl, lower alkylsulfonyl, lower alkoxycarbonyloxy, succinimido, glutarimido, or phthalimido.

The azo compounds of formula (II) possess exceptional dyeability and exhibit particularly good brightness and fastness properties when applied to polyester textile materials. These compounds conform to the formula in wherein V is chlorine, bromine or cyano;

A is lower alkanoyl, benzoyl, lower alkoxycarbonyl, lower alkylcarbamoyl;

R is methyl or, when R and R each is hydrogen, lower alkyl;

R and R each is hydrogen or methyl; and

R is lower alkyl, benzyl, or a substituted alkyl group having the formula -R' -R wherein R is ethylene or propylene, and R is lower alkoxy, lower alkanoyloxy, cyano, carbamoyl, lower alkanoylamino, or lower alkylsulfonyl.

The novel azo compounds are prepared by diazotizing an amine having the formula D-NH and coupling the diazotized amine with a compound having the formula according to known procedures. The compounds of formula (III) are obtained by methods analogous to published procedures employing known reactants. For example, a l,2,3,4-tetrahydroquinoline can be nitrated by treatment with nitric acid in the presence of sulfuric acid. The 7-nitro compound can then be reduced to the 7-amino compound which is then acylated according to known procedures. The ring nitrogen atom of the tetrahydroquinoline can be alkylated before or after nitration, reduction and acylation, using alkylating agents such asacrylonitrile, ethyl bromide, benzyl chloride, isobutyl bromide, methyl vinylsulfone, methylacrylate, triethyl phosphate, p-methoxybenzyl chloride, etc. Such tetrahydroquinoline compounds can also be alkylated by reacting a tetrahydroquinoline with an epoxide resulting in an N-hydroxyalkyltetrahydroquinoline which can be treated further with .other compounds such'as halogenating and acylating agents. Suitable epoxides include ethylene oxide, epichlorohydrin, l,2-epoxy-3-methoxypropane, 1,2- epoxy-3-phenoxypropane, propylene oxide, etc. The novel azo compounds having a cyano group ortho to the azo groups also can be prepared by reacting the analogous o-halo compound with cuprous cyanide in a variety of solvents according to known techniques.

The following examples describe typical procedures by which the couplers of formula (111) can be prepared EXAMPLE A l-Ethyl-2,2,4-trimethyl l ,2,3,4-tetrahydroquinoline (96.5 'g.) is added slowly to 500 ml. of concentrated H,SO at about 5 C. Then a solution of 33 ml. concentrated HNO and 33 ml. concentrated H SO is added dropwise at 05 C. The reaction is stirred 0.5 hr. longer after the addition is completed and then drowned in ice-water mixture. After the mixture is made basic with concentrated ammonium hydroxide, the product is taken up in hexane and toluene and washed with water. The solvent is evaporated to leave 'the 7-nitro compound as a semi-solid, mass. The nitro compound (105 g.) is dissolved in 1,250 ml. of 28 alcohol and hydrogenated in the presence of Raney nickel at 75 C. and about 1500 psi. hydrogen pressure. The catalyst is filtered off and the filtrate evaporated to yield 7-amino-1-ethyl-2,2,4-trimethyl-1,2,3,4- tetrahydroquinoline in the form of a black viscous oil. The 7 amino compound (21.8 g.) is dissolved in 30 ml.

'of acetic acid. Acetic anhydride (10 ml.) is added, and

the reaction is allowed to stand for 1 hr. and then drowned in water. The product, 7-acetamido-l-ethyl- 2,2,3-trimethyl-l,2,3,4-tetrahydroquinoline, solidifies on standing, is collected by filtration and recrystallized from water-methanol solution. M.P.: l23-127 C.

Analysis:

Theory'forCmH N- oz C, 73.8; H, 9.3; N, 10.8 Found:C,73.5;H,9.0;N,10.8

EXAMPLE B -7-Aminol -ethyl-2,2,4-trimethyl-l ,2,3 ,4- tetrahydroquinoline is benzoylated' using benzoyl chloride in pyridine to yield 7-benzamido-1-ethyl-2,2,4 trimethyl-l,2,3,4-tetrahydroquinoline which melts at l79-l82C.

EXAMFLE C 7 Amino- 1 -ethyl-2,2,4-trimethyl- 1 ,2,3 ,4-

tetrahydroquinoline is reacted with phenyl isocyanate in benzene to yield lethyl-7phenylcarbamoylamino- 2,2,4-trimethyl 1,2,3,4-tetrahydroquinoline having a melting point of l65-175 C.

Analysis:

Theory for C H N O: C, 74.8; H, 8.1; N, 12.5

Found: C, 75.2; H, 8.1; N, 12.6.

' EXAMPLE D 7-Nitro-1,2,3,4-tetrahydroquinoline (2.7 g.), benzyl chloride (2.2 g.), and N,N-dimethylformamide (25 ml.) are heated and stirred at 140-l45 C. for 5 hr. The reaction is drowned in water and basified by the addition of NH.,OH. The product is taken up in benzene-hexane and washed with water. The solvent is evaporated to yield the product, N-bcnzyl-7-nitrol,2,3,4-tetrahydroquinoline. The nitro compound is reduced to the amine by hydrogenating in the presence of Raney nickel catalyst as in Example A above.

7-Amino-N-benzyl-l,2,3,4-tetrahydroquinoline (2.9 g.) is mixed with 2 ml. of acetic acid, plus 2 ml. of acetic anhydride and heated 0.5 hr. in steam bath. On cooling, the product, 7-acetamido-l-benzyl-1,2,3,4- tetrahydroquinoline, solidifies and is filtered and recrystallized from methanol, It melts at 145-147 C.

The substitution of other acylating and alkylating agents in the procedures described in the preceding example yields various other couplers of formula (III).

Examples of other acylating agents which can be used are as follows: methanesulfonyl chloride, ptoluene sulfonyl chloride, p'ropionic anhydride, butyric anhydride, isobutyric anhydride, chloroacetyl chloride, methoxyacetyl chloride, phenoxyacetyl chloride, cyclohexanecarbonyl chloride, methylthioacetyl chloride, methylsulfonylacetyl chloride, p-methoxybenzoyl chloride, ethyl isocyanatc, n-butyl isocyanatc,

chloroethyl isocyanatc, cyclohexyl isocyanate, ethyl chloroformate, methyl chloroformate, n-butyl chloroformate, and cyclohexyl chloroformate.

The preparation of the novel azo compounds is further illustrated by the following examples.

EXAMPLE 1 2-Cyano-4,6-dinitroaniline (2.08 g.) is slurried in 35 ml. of H 80, at 15 C. The mixture is cooled to 2 C. and a solution of 0.72 g. sodium nitrite in 5 ml. of cone. H SO is added at 2 to 0 C. The reaction mixture is stirred at 0 C. for 2 hrs. and is then added to a solution of 2.60 g. 7-acetamido-l-ethyl-2,2,4- trimethyl-l,2,3,4-tetrahydroquinoline dissolved in 100 ml. of conc. H at below 10 C. After coupling for 1 hr., the dye is precipitated by drowning in water. The product is collected by filtration, washed with water, and air dried. The product, 6-(2-cyano-4,6- dinitrophenylazo)-7-acetamido-1 ethyl-2,2,4- trimethyl-l,2,3,4-tetrahydroquinoline, produces a bright greenish-blue shade on polyester fibers and has excellent light-fastness and resistance to sublimation.

EXAMPLE 2 The procedure described in Example 1 is repeated except that 3.22 g. 7-benzarnido-l-ethyl-2,2,4- trimethyl-l ,2,3,4-tetrahydroquinoline is substituted for the coupler employed in Example 1. The product ob tained, 6-(2-cyano-4,6-dinitrophenylazo)-7- benzamido-1-ethyl-2,2 ,4-trimethyl-1,2,3 ,4- tetrahydroquinoline, produces a bright blue shade on polyester fibers.

EXAMPLE 3 The compound 6-(2-cyano-4,6-dinitrophenylazo)-7- acetamido-l-benzyl-2-methyl-1,2,3 ,4-tetrahydroquinoline, prepared by diazotizing 2.08 g. 2-cyano-4,6- dinitroaniline and coupling with 2.80 g. 7-acetamido-lbenzyl-2-methyl-l,2,3,4-tetrahydroquinoline according to Example 1, produces bright blue shades on polyester fibers.

EXAMPLE 4 2-Cyano-4,6-dinitroaniline (2.08 g.) is diazotized and coupled with 7-acetamido-l-(2-succinimidoethyl)- 2,2,4-trimethyl-l,2,3,4-tetrahydroquinoline (3.57 g.) according to the procedure employed in Example 1. The dye obtained, 6-(2-cyano-4,6-dinitrophenylazo)-7- acetamido-l-(2-succinimidoethyl)-2,2,4-trimethyll,2,3,4-tetrahydroquinoline, dyes polyester fiber bright blue and has outstanding sublimation fastness.

EXAMPLE To 5 ml. of conc. 1-1 SO is added 0.72 g. dry NaNO portionwise. The solution is cooled and 10 ml. of 1:5 acid (1 part propionic:5 parts acetic acid) is added below C. The mixture is cooled again and 2-bromo- 4,6-dinitroaniline (2.62 g.) is added, followed by 10 ml. additional 1:5 acid, all at 0-5 C. After stirring at 0-5 C. for 1 hr. the diazonium solution is added to a solution of 2.60 g. 7-acetamido-l-ethy1-2,2,4-trimethy1- l,2,3,4-tetrahydroquinoline in 100 ml. of cone. H 80 below 10? C. After allowing to stand for 1 hr. at below 10 C., the coupling mixture is drowned into water. The blue product is collected by filtration, washed with 8 water, and dried in air. The az o compound obtained 4- (2-bromo-4,o dinitrophenylazo) 7-acetamido-l-ethyl- 2,2,4-trimethyl-l,2,3,4-tetrahydroquinoline, produces bright blue shades on polyester fibers. The analogous 2- chloro dye obtained from 2-chloro-4,o-dinitroaniline also imparts fast blue shades to polyester fibers.

EXAMPLE 6 2-Chloro-4,6-dinitroaniline (2.17 g.) is diazotized and coupled with 3.22 g. of 7-benzamido-l-ethyl-2,2,4- trimethyl-l,2,3,4-tetrahydroquinoline according to the procedure described in Example 5. The product, 6-(2- chloro-4,o-dinitrophenylazo)-7-benzamido-1-ethyl- 2,2,4-trimethy1-l,2,3,4-tetrahydroquinoline produces blue shades of excellent fastness to light and sublimation on polyester fibers.

EXAMPLE 7 Sodium nitrite (0.72 g.) is added portionwsie to 5 ml. of concentrated sulfuric acid. The solution is cooled and 10 ml. of 1:5 acid is added below 15 C. The mixture is cooled further and 2.5 g. 2,4-bis(methylsulfobelow 5 C. After stirring for 2 hrs. at 0-5 C., the diazonium solution is added to a chilled solution (below 5C.) of 3.26 g. 1-(2-acetoxyethyl)-2-methyl-7- methylsulfonamido-l,2,3,4-tetrahydroquinoline in ml. of 15 percent sulfuric acid below 5 C. The reaction is kept cold and ammonium acetate is added until the coupling mixture is neutral to Congo Red test paper. After allowing to couple for 1 hr. at about 5 C., the reaction mixture is drowned in water. The product is collected by filtration, washed with water, and dried in air. The product, 6-[2,4-bis(methylsulfonyl)phenylazo 1 acetoxyethyl )-2-methyl-7-methylsulfonamidol,2,3,4-tetrahydroquinoline, produces fast red dyeings on polyester fibers.

The compounds described in the examples appearing in the Table are prepared according to the procedures described in the preceding examples and conform to formula (I). The color given for each compound is the shade produced on polyester fibers by the compound.

ing agents such as surfactants, dispersing agents, car

riers, thicken'ers, etc. The dyeing can be carried out at the boil at atmospheric pressures or at higher temperatures under pressures moderately above atmospheric pressures. The following example illustrates a carrier dyeing procedure for applying the aao compounds of theinvention to polyester textile materials.

EXAMPLE 193 The azo compound of Example 1 (-0.1 g.) is dis solved in cc. of 2-me thoxyethanol. A small amount (3-5 cc.) of a 3 percent sodium lignin sulfonate aqueous solution is added, with stirring, and then the volume of the bath is brought to 300 cc. with water. 3 cc. of an anionic solvent carrier (Tanavol) is added to the bath and 10 g. of a textile fabric made of poly- (ethylene terephthalate) fibers isplaced in the bath and worked 10 minutes without heat. The dyeing is carried out at the boil for 1 hour. The dyed fabric is removed from the dyebath and scoured for 20 minutes at 80 C. in a solution'containing 1 g./L. neutral soap and 1 g./L. sodium carbonate. The fabric is then rinsed, dried'in an oven at 250 F. and heat set (for removal of residual carrier) for 5 minutes at 350 C.

The compounds of the invention can also be applied to polyester textile materials by the heat fixation technique described in U. S. PaLNo. 2,663,612 and in the American Dyestuff Reporter, 42, l (1953). The following procedure describes how the azo compounds of the invention can be applied to polyester materials by the heat fixation technique.

EXAMPLE 194 A mixture of: 500 mg. of the compound of Example 3, 150 mg. ofa

.sodium lignosulfonate dispersing agent (Marasperse N), 150 mg. of a partially desulfonated sodium lignosulfonate (Marasperse CB), 0.5 ml. glycerin, and 1.0 ml. of water is ground in a microsize container (an accessory for a l-quart size Szegvari Attritor) for approximately 3.5 hours. Enough l/8-inch stainless steel balls are added to provide maximum grinding. When the grinding is complete, the entire contents are poured I to 100 ml. The thickener and penetrating mixture is added to the dye paste, the volume is adjusted to 200 ml. and the mixture is agitated for minutes. The dye mixture is then filtered through folded cheesecloth to remove the stainless steel balls and it then is added to the reservoir of a Butterworth padder where it is heated toabout 4560 C.

10 g. of a fabric of poly(ethylene terephthalate) fibers and 10 g. of a fabric of 65/35 spun poly(ethylene terephthalate)/cotton fibers are sewn together, end-toend, and padded for 5 minutes of continuous cycling through the dye mixture and between three rubber squeeze rollers of the padder. Dye mixture pickup is about 60 percent based on the weight of the fabrics.

' The paddedfabrics are then dried at 200 F. and then heat-fixed for 2 minutes at 415 F. in a forced air oven.

' tion when tested according to the procedures described The dyed fabrics are scoured for 20 minutes at 6570 C. in a solution containing 0.2 percent sodium hydrosulfite, 0.2 percent sodium, carbonate and 1.7 percent of a 3 percent solution of sodium N-methyl-N- oleoyltaurate and then dried. The dyed fabrics possess excellent brightness and fastness to light and sublimalinear polyester textile materials that can be dyed with the compounds ofthe invention are those prepared from ethylene glycol and dimethylterephthalate or from cyclohexanedimethanol and dimethylterephthalate. Polyesters prepared from cyclohexanedimethanol I and dimethylterephthalate are 'more' particularly described in 'U. S. Pat. No. 2,901,446. Poly(ethylene terephtalate) polyester fibers are described, for example, in U. S. Pat. No. 2,465,319. The polymeric linear polyester materials disclosed in U. S. Pat. Nos. 2,945,010, 2,957,745 and 2,989,363, for example, can be dyed. The linear aromatic polyester materials specifically named have a melting point of at least 200 C. The poly(ethylene terephthalate) fibers which are dyed with the compounds of the invention are manufactured from a melt of a polymer having an inherent viscosity of at least 0.35 and preferably, about 0.6. The inherent viscosity of the poly(1,4-cyclohexylenedimethylene terephthalate) polymer is also at least 0.35. These inherent viscosities are measured at 25 C. using 0.25 g. polymer per ml. of a solvent consisting of 60 percent phenol and 40 percent tetrachloroethane. The polyester fabrics, yarns, fibers and filaments that are dyed with the novel azo compounds can also contain minor amounts of other additives such as brighteners, pigments, delusterants, inhibitors, stabilizers, etc. Although the azo compounds of the invention are particularly. suitable for dyeing polyester textile materials, they can also be used to dye other hydrophobic textile materials such as cellulose acetate and polyamide fibers.

riis'raven tfifiayssn assessed" 'iii' 'corisid'iab l detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

We claim: V bamoyloxy, chlorophenylcarbamoyloxy or 1. A linear polyester textile fiber dyed with an azo bromophenylcarbamoyloxy. compound having the formula 2. A dyed textile fiber according to claim 1 wherein the polyester is poly(ethylene terephthalate) or g poly(l,4-cyclohexylenedimethylene terephthalate).

3. A dyed textile fiber according to claim 2 wherein DN:N the azo compound has the formula I ANH. I -R X R4 I Nc N:N- A u I k wherein v i 7 I Y \N D is a phenyl radical having the structure I R H' v Y 0 'Y wherein O- Y and Y each is hydrogen, cyano, chlorine, or

n I r bromine' RSO 1 I i A is lower alkanoyl, benzoyl, or lower alkoxycarbon- A R is methyl or, when R and R each is hydrogen, wherein lower alkyl;

V is chlorine, bromine, cyano, lower alkanoyl, R1 3 R3 each hydrogen or methyl; and

benzoyl, lower alkylbenzoyl, lower alkoxybenzoyl, R5 lower y p y f 9 a group chlorobenzoyl, bromobenzoyl, lower alkylsulfonyl, havmg the fol'mula wherein R ethylene or trifluoromethyl; or propylene, and R 18 lower alkanoyloxy, lower X is nitro or cyano; alkoxy, lower alkanoylamino, cyano, carbamoyl, Y and Y are the same or different and each is y h ny y, SUCClhlmldO, g hydrogen, cyano, chlorines or bromine; tahmldo, 0T p h Z i h d cyano, hl i b i lower 4. A dyed textile fiber according to claim 2 where:

k l lf l; d the azo compound has the formula R is lower alkyl; 7 m a A is formyl; lower alkanoy]; lower alkanoyl substituted with chlorine, bromine, Ar, cyano, lower msor N....N:@

alkoxy, lower alkylthio, lower alkylsulfonyl, or R1 benzyloxy; ArCO; cyclohexylcarbonyl; lower alz A-IIN koxycarbonyl; lower alkoxycarbonyl substituted R with cyano, hydroxy, or halogen; ArOOC-; R5

cyclohexoxycarbonyl; lower alkylsulfonyl; lower 40 alkylsulfonyl substituted with cyano, hydroxy, wherem chlorine, or bromine; cyelohexylsulfonyl; ArSO Z is y g chlorine, bromine, lower l yl lcarbamoyl, lower alkylcarbamoyl; ArNHCO-; y; sulfam oyl; lower alkylsulfamoyl; or ArNHSO R is lower y wherein Ar i h l or h l b i d i h A is lower alkanoyl, benzoyl, or lower alkoxycarbonlower alkyl, lower alkoxy, chlorine, or bromine; y R, R and R are the same or different and each is R is methyl when and R3 each is y g hydrogen or lower alkyl; lower alkyl; R is hydrogen, lower alkoxy, or lower alkanoyloxy; R and R each is hydrogen or m thy and R is hydrogen, lower alkyLorlower alkoxy; and R is lower alkyl, benzyl, Z-phenylethyl, or a group R is alkyl containing one to about six carbon atoms; having the formula wherein R iS ethylene 0r benzyl; benzyl substituted with lower alkyl, lower p py and R9 is lower y y, lower alkoxy, chlorine or bromine; Z-phenylethyl; 2- ROXY, 'Q alkanoylamino, y carbamyl, phenylethyl substituted with lower alkyl, lower allower lkoxy nyl xy, CCiIIimidO, glukoxy, chlorine or bromine; cyclohexyl; or a group tarimido, or phthahmidohaving th f rm l R -R h i R i h l 5. A dyed textile fiber according to claim 2 wherein or propylene, and R is lower alkanoyloxy, lower the azo compound has the formula alkoxy, lower alkoxycarbonyl, lower alv 3 kanoylamino, cyano, carbamyl, lower alkylsulfonyl, lower alkylsulfonamido, lower alkoxycarbon- 0 N -N=::N yloxy, succinimido, glutarimido, phthalimido, benzamido, lower alkylbenzamido, lower alkoxy X ArNu" \N R .benzamido, chlorobenzamrdo, bromobenzamldo,

phenoxy, lower alkylphenoxy, lower alkoxyphenoxy, chlorophenoxy, bromophenoxy, lower wherein alkylcarbamoyloxy, phenylcarbamoyloxy, lower V is chlorine, bromine, cyano, or benzoyl; alkylphenylcarbamoyloxy, lower alkoxyphenylcar- X is nitro or cyano;

33 34 A is lower alkanoyl, benzoyl, or alkoxycarbonyl; 8. A dyed textile fiber according to claim 2 wherein R is methyl or, when R and R each is hydrogen, the azo compound has the formula lower alkyl; NO can.

R and R each is hydrogen or methyl; and I l R is lower alkyl, benzyl, 2-phenylethyl, or a group 5 having the formula -R-R wherein R is ethylene or propylene, and R is lower alkanoyloxy, lower 6N NH g alkoxy, lower alkanoylammo, cyano, carbamoyl, 8 3 CH: lower alkoxycarbonyloxy, succinimido, glu- 7 tarimido, or phthalimido. l

6. A dyed textile fiber according to claim 2 wherein the azo compound the formula 9. A dyed textile fiber accordingto claim 2 wherein th dh m f l Q eazo compoun as e ormu a N02 A-NH N CH v J: I

- I N NII \N -om V is chlorine, bromine, or cyano;

wherein a I g AJHF A is lower alkanoyl; R and R each is hydrogen or methyl; and

R is lower alkyl, benzyl, or a group having the formula -R*-R wherein R is ethylene or propylene,

10. A dyed textile fiber according to claim 2 wherein the azo compound has the formula and R is lower alkoxy, lower alkanoyloxy, cyano, NO on: carbamoylv or lower alkan'oylamino. 7. A dyed textile fiber according to claim 2 wherein 01N'N:N the azo compound has the formula k W V V V" (1 NH \N 6:0

, I ITIQ2 (IJIIz 2H:

&

N NH 

1. A linear polyester textile fiber dyed with an azo compound having the formula
 2. A dyed textile fiber according to claim 1 wherein the polyester is poly(ethylene terephthalate) or poly(1,4-cyclohexylenedimethylene terephthalate).
 3. A dyed textile fiber according to claim 2 wherein the azo compound has the formula wherein Y and Y'' each is hydrogen, cyano, chlorine, or bromine; A is lower alkanoyl, benzoyl, or lower alkoxycarbonyl; R is methyl or, when R1 and R3 each is hydrogen, lower alkyl; R1 and R3 each is hydrogen or methyl; and R5 is lower alkyl, benzyl, 2-phenylethyl, or a group having the formula -R8-R9 wherein R8 is ethylene or propylene, and R9 is lower alkanoyloxy, lower alkoxy, lower alkanoylamino, cyano, carbamoyl, lower alkoxycarbonyloxy, succinimido, glutarimido, or phthalimido.
 4. A dyed textile fiber according to claim 2 wherein the azo compound has the formula wherein Z is hydrogen, chlorine, bromine, or lower alkylsulfonyl; R6 is lower alkyl; A is lower alkanoyl, benzoyl, or lower alkoxycarbonyl; R is methyl or, when R1 and R3 each is hydrogen, lower alkyl; R1 and R3 each is hydrogen or methyl; and R5 is lower alkyl, benzyl, 2-phenylethyl, or a group having the formula -R8-R9 wherein R is ethylene or propylene, and R9 is lower alkanoyloxy, lower alkoxy, lower alkanoylamino, cyano, carbamoyl, lower alkoxycarbonyloxy, succinimido, glutarimido, or phthalimido.
 5. A dyed textile fiber according to claim 2 wherein the azo compound has the formula wherein V is chlorine, bromine, cyano, or benzoyl; X is nitro or cyano; A is lower alkanoyl, benzoyl, or alkoxycarbonyl; R is methyl or, when R1 and R3 each is hydrogen, lower alkyl; R1 and R3 each is hydrogen or methyl; and R5 is lower alkyl, benzyl, 2-phenylethyl, or a group having the formula -R8-R9 wherein R8 is ethylene or propylene, and R9 is lower alkanoyloxy, lower alkoxy, lower alkanoylamino, cyano, carbamoyl, lower alkoxycarbonyloxy, succinimido, glutarimido, or phthalimido.
 6. A dyed textile fiber according to claim 2 wherein the azo compound has the formula wherein V is chlorine, bromine, or cyano; A is lower alkanoyl; R1 and R3 each is hydrogen or methyl; and R5 is lower alkyl, benzyl, or a group having the formula -R8-R9 wherein R8 is ethylene or propylene, and R9 is lower alkoxy, lower alkanoyloxy, cyano, carbamoyl or lower alkanoylamino.
 7. A dyed textile fiber according to claim 2 wherein the azo compound has the formula
 8. A dyed textile fiber according to claim 2 wherein the azo compound has the formula
 9. A dyed textile fiber accordiNg to claim 2 wherein the azo compound has the formula 